JPH0155308B2 - - Google Patents

Description

[Detailed description of the invention]

The subject of the present invention is the general formula A[(X-O)n-H]m, where A represents rosin or disproportionated rosin, phenol, guaiacol, salicylic acid, o-, m-
and an aromatic hydroxy compound selected from the group consisting of p-cresol and β-naphthol, or selected from the group consisting of 4-chlorophenol, 5-chloro-2-hydroxytoluene, 4-chloro-1-naphthol and benzyl chloride. indicates the residue of a natural resin acid modified by oxyarylation obtained by reacting a halogen-eliminating aryl- or aralkyl-compound with the addition of a polycyclic system to the double bond; or represents a residue of a glycerin ester of these modified natural resin acids, where X is a group of the formula _-CH2CH2- , n is a number from about 3 to ₄₀ , and the total number of n is a number from about 8 to 75. m is 2 or 3). The subject of the invention is also to prepare natural resin acid derivatives of the general formula A-(H)m, in which A and m have the meaning given above, and free hydroxy- and optionally hydroxy- The process is characterized in that a compound having a group is reacted with nm mol (n and m have the meanings given above) of ethylene oxide under etherification or esterification of the functional group. A further object of the invention is the use of the natural resin acid derivatives mentioned above as surfactants. They are obtained by reaction with aralkyl or aryl compounds by known methods and optionally esterification with glycerin. Suitable modified resins can be modified in an organic medium in the presence of strongly acidic or acid-eliminating catalysts such as boron trifluoride, hydrogen chloride, tin tetrachloride, aluminum chloride or mineral acids.
Phenol, o-, m- or p- at a temperature of 120°C
Cresol, salicylic acid, guaiacol, and β-naphthol are combined with natural resin acids such as abietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, levopimaric acid,
dextropimaric acid and isodextropimaric acid (e.g. these are present in commercially available rosins) and disproportionated resin acids, preferably 0.5 to 1.0, preferably 0.7-, per mole of resin acid.
Resin-phenol derivatives such as those obtained using 0.8 mol of the above phenols or naphthols. Additionally, in the presence of a catalyst such as zinc chloride approximately 0.2% 100
The natural resin acid is treated at a temperature of from 150 to 210°C, preferably from 150 to 210°C, with a halogen-eliminating aryl- or aralkyl-compound such as benzyl chloride, 4-chlorophenol, 5-chloro-2-hydroxytoluene, 4-chloro-1 - react with naphthol,
Suitable here are modified natural resin acids, such as those obtained using advantageously 0.5 to 1.0 mol, preferably 0.7 to 0.8 mol, of the abovementioned halogen-eliminating compounds per mol of resin acid. Preferred modified resins are therefore preferably phenyl- or naphthyl residues, which are optionally linked via methylene groups (these may be hydroxy-, lower-alkyl-, lower-alkoxy-, carboxy-, phenyl- or hydroxyalkyl-groups). They can be substituted, in which case the hydroxy and carboxy groups introduced in this way are likewise alkoxylated). Esterification of modified resin acid with glycerin is 1:
1 to 4:1, preferably 1:1 to 2:1, by known esterification methods at 180 to 300°C, preferably 200 to 270°C, optionally adding an extrusion agent such as an aromatic hydrocarbon or a chlorohydrocarbon. Done below. Examples of catalysts include benzenesulfonic acid,
p-Toluenesulfonic acid, boric acid, tin powder or sulfuric acid can be used. The reaction of modified natural resin acids and their esterification products with ethylene oxide is carried out by known methods, preferably using an alkali hydroxide or -alkoxide as a catalyst, at 100 to 200°C, especially 140°C to 180°C.
Performed at °C. Potassium hydroxide or especially sodium hydroxide is suitable as the alkali hydroxide, and sodium methylate or -ethylate is suitable as the alkali alkoxide. The catalyst concentration is between 0.05 and 1.0% by weight, based on the starting product. The oxyethylation can be carried out in pressure-free or pressurized vessels using ethylene oxide or a mixture of both components, the ethylene oxide being able to be added in gaseous or liquid form. As long as it is carried out under pressure, the working pressure is 1 to 10
Preference is given to an overpressure of 2 to 8 bar. The amount of ethylene oxide is proportioned such that stable emulsification or sufficient solubility of the addition product in water is achieved. In particular, the free carboxy and hydroxy groups of each of the modified natural resin acids or the esterification products of these modified natural resin acids contain
100, preferably 8 to 75 moles of ethylene oxide are added. The amount of ethylene oxide added depends on the intended use and therefore also on the degree of hydrophilicity sought to be obtained. The starting products obtained by the addition of phenols to natural resin acids are known and have been used in the preparation of radsker (West German Patent Specification No. 536 170, No. 581 956, No.
582846 and 652602), while the starting product obtained by reaction of a natural resin acid with a halogen-eliminating aryl- or aralkyl-compound and subsequent esterification with an alcohol is an oil-soluble synthetic resin. (West German Patent Specification No. 570958). Furthermore, it is known to oxyethylate rosins, giving detergents, emulsifiers and leveling agents (Ullmanns Encyklopadie der technischen).
Chemie 3rd edition, Volume 8, P.409). The oxyethylated products according to the invention and/or their mixtures give water-stable emulsions or are clearly soluble in water and are suitable for the ring-cleavage process according to DIN 53914.
According to the Ross-Miles test (DIN No. 53902), there is almost no foaming. They wet cotton fabrics by the dip-wetting method (DIN 53901) within 70 to 180 seconds and are stable to strong alkalis as well as strong acids under the usual conditions of use of surfactants. Its inherent color is very pale to virtually colorless as an aqueous solution. The compounds according to the invention can be used as dispersants, wetting agents and distribution agents (e.g. for pigments and also for the formulation of plant protection and pest control agents) and as emulsifiers for the production of carrier emulsions and for natural and synthetic fiber materials, e.g. cotton, wool, cellulose, cotton yarn,
They are eminently suitable as leveling agents and dyeing aids in the dyeing and printing of cellulose acetates and triacetates, polyesters, polyamides and polyacrylonitrile or textile materials containing these materials. The advantages of the substances according to the invention over the known non-ionic compounds consist in a significantly improved dispersion behavior in the aqueous range of use and, despite good wetting properties, almost no foaming power. . The new products are also easily biodegradable. The natural resin acid derivatives according to the invention are used alone or in mixtures or in combination with other nonionic and anionic or cationic active compounds, builders and other additives and auxiliaries in emulsifying and dispersing agent formulations. can do. The following examples describe the preparation of natural resin acid derivatives according to the invention. Unless stated otherwise, parts and percentages relate to weight and pressure statements relate to overpressure. The acid number (SZ) is determined according to DIN No. 53185. Example 1 (a) Preparation of resin-phenol derivatives 173.8 parts of a 25% solution of boron trifluoride in phenol was mixed with 800 parts of tetrachloromethane at 10°C within 4 hours.
Add 604 parts of rosin to the solution and add to the solution for 15 hours for 14 hours.
Post-stir at 18°C. To remove the catalyst, the reaction mixture is washed neutral with water and dried over anhydrous sodium sulfate. Tetrachloromethane is subsequently removed by distillation. 630 parts of a transparent resin having an acid number of about 114 and a softening point of about 105° C. are obtained. (b) Preparation of resin-oxyalkylate 367 parts of the modified resin described in (a) are stirred in an airtight container after adding 1.5 parts of sodium hydroxide and fed with 378.4 parts of ethylene oxide at 150 to 170°C under a pressure of 1.5 to 2.5°C. Oxyethylate under crowbar hold. When all ethylene oxide is injected, 1
Post-stir at 150-160° C. for an hour. A viscous brown resin-oxyethylate is obtained which contains 8.6 moles of ethylene oxide and has a cloud point of 56.5 DEG C. in 25% butyl diglycol solution. Example 2 367 parts of the resin prepared according to Example 1(a) are stirred in a gas-tight container after addition of 1.5 parts of sodium hydroxide and heated at a pressure of 150 to 170° C. while feeding 2200 parts of ethylene oxide.
Oxyethylation is carried out under a maintenance pressure of 1.5 to 2.5 bar.
150 for 1 hour when all ethylene oxide is injected
Post-stir at 160°C. The waxy resin-oxyethylate obtained is ocher in color and contains 50 moles of ethylene oxide. Its cloud point in aqueous solution is about 60°C. Example 3 367 parts of the resin produced according to Example 1(a) were stirred in an airtight container after adding 1.5 parts of sodium hydroxide and fed with 3300 parts of ethylene oxide at a pressure of 150 to 170°C.
Oxyethylation is carried out under a maintenance pressure of 1.5 to 2.5 bar.
When all the ethylene oxide is forced in, it is then stirred for 1 hour at 150-160°C. The resulting resin-oxyethylate contains 75 moles of ethylene oxide and corresponds in appearance to the product of Example 2. The cloud point is
25% butyl diglycol solution at 101-102°C. Example 4 (a) Preparation of resin-guaiacol-derivatives 25% solution of boron trifluoride in guaiacol 264.5
of tetrachloromethane at 10°C within 4 hours.
Add to a solution of 604 parts of rosin in 800 parts and for 14 hours
Post-stir at 15-18°C. After working up according to Example 1, 630 parts of a transparent resin having an SZ (acid number) of about 101 and a softening point of about 110 DEG C. are obtained. (b) Preparation of resin-oxyethylate 367 parts of the modified resin described in (a) are stirred in an airtight container after adding 1.5 parts of sodium hydroxide and fed with 2200 parts of ethylene oxide at 150-170°C under a pressure of 1.5-2.5. Oxyethylation under maintenance of bar. When all the ethylene oxide is injected, it is stirred for 1 hour at 150-160°C. The resulting brown resin-oxyethylate is waxy and contains 50 moles of ethylene oxide. The cloud point in aqueous solution is 97°C. Example 5 After adding 1.5 parts of sodium hydroxide to 868.5 parts of the modified resin prepared according to Example 4(a), stirring in an airtight container and feeding 3300 parts of ethylene oxide at 150 to 170°C.
oxyethylation at a pressure of 1.5 to 2.5 bar. 1 hour when all ethylene oxide is injected
Post-stir at 150-160°C. The waxy resin obtained
The oxyethylate is ocher in color and contains 75 moles of ethylene oxide. The cloud point in an aqueous solution is 96.5°C. Example 6 (a) Production of resin-salicylic acid derivative 174 parts of boron trifluoride-ethyl ether complex salt
It is added within 4 hours at 10.degree. C. to a solution of 604 parts of rosin and 220.8 parts of salicylic acid in 600 parts of tetrachloromethane and stirred for 14 hours at 15.degree.-18.degree. After post-treatment according to Example 1, the SZ is approximately 173 and the softening point is approximately
710 parts of transparent resin having a temperature of 115-120°C are obtained. (b) Preparation of resin-oxyethylate 412.4 parts of the modified resin described in (a) is stirred in an airtight container after adding 1.5 parts of sodium hydroxide and fed with 1100 parts of ethylene oxide at 150 to 170°C under a pressure of 1.5 to 2.5%. Oxyethylation under maintenance of bar. When all ethylene oxide is injected, 1
Post-stir at 150-160° C. for an hour. The resulting waxy brown resin-oxyethylate contains 25 moles of ethylene oxide and has a cloud point in 10% saline solution of 49.5°C. Example 7 (a) Production of resin-naphthol derivative 106 parts of boron trifluoride-ethyl ether complex salt
It is added within 4 hours at 10 DEG C. to a solution of 604 parts of rosin and 203.2 parts of β-naphthol in 600 parts of tetrachloromethane and stirred for 14 hours at 15 DEG -18 DEG C. After working up according to Example 1, 726.3 parts of a transparent resin are obtained having an SZ of about 145 and a softening point of about 115-120 DEG C. (b) Preparation of resin-oxyethylate 403.6 parts of the modified resin described in (a) is mixed with 3.0 parts of sodium methylate in an airtight container, stirred and fed with 2200 parts of ethylene oxide for 160 to 180 hours.
Oxyethylation is carried out at a pressure of 2 to 8 bar. The post-stirring time at 150-160°C is 1 hour. The resulting waxy yellow-brown resin oxyethylate contains 50 moles of ethylene oxide and has a cloud point of 95.5° C. in 25% butyl diglycol solution. Example 8 (a) Preparation of resin-phenol derivatives 173.8 parts of a 25% solution of boron trifluoride in phenol are added within 4 hours at 10° C. to a solution of 604 parts of rosin in 800 parts of tetrachloromethane and for 14 hours 15-18 Post-stir at ℃. After working up according to Example 1, about 630 parts of SZ114 and a transparent resin with a softening point of about 105° C. are obtained. (b) Preparation of resin-phenol glycerin ester 367 parts of the resin-phenol compound described in (a) is heated to 230°C within 8 to 10 hours while distilling off the reaction water in a stirred vessel in the presence of 5 parts of tin powder. Esterify 92 parts of glycerin and SZ to about 25 at 250° C. under simultaneous nitrogen flow. (c) Production of resin-phenol glycerin ester-oxyethylate 438 parts of resin-phenol glycerin ester described in (b) was added with 3.3 parts of sodium ethylate, then stirred in an airtight container and heated with ethylene oxide.
Oxyethylation is carried out at 150-160° C. and maintaining a pressure of 2-3 bar while feeding 440 parts. When all the ethylene oxide is forced in, it is then stirred for 1 hour at 150-160°C. 10 moles of ethylene oxide and 25%
A viscous brown resin - glycerin ester - with a cloud point of 56.5°C in butyl diglycol solution
Oxyethylate is obtained. Example 9 (a) Preparation of resin-cresol derivatives 25% solution of boron trifluoride in industrial cresol
200 parts are added within 4 hours at 10.degree. C. to a solution of 604 parts of rosin in 800 parts of tetrachloromethane and stirred for 14 hours at 15.degree.-18.degree. After working up according to Example 1, 767 parts of a transparent resin of SZ117 and a softening point of about 105° C. to 110° C. are obtained. (b) Preparation of resin-cresol-glycerin ester 377 parts of the resin-cresol compound described in (a) was heated at 230°C within 8 to 10 hours in the presence of 5 parts of tin powder in a stirred vessel while distilling off the reaction water. Esterify with 92 parts of glycerin to about 25 SZ at a temperature of 250°C to 250°C while simultaneously passing nitrogen gas. (c) Production of resin-cresol-glycerin ester-oxyethylate 451 parts of the resin-cresol-glycerin ester described in (b) are oxyethylated with 440 parts of ethylene oxide after addition of 3.3 parts of sodium methylate. The resulting brown resin ester adduct is viscous and contains 10 moles of ethylene oxide. The cloud point of a 25% butyl diglycol solution is
It is 60℃. Example 10 (a) Preparation of resin-phenol derivatives 173.8 parts of a 25% solution of boron trifluoride in phenol was mixed with 800 parts of tetrachloromethane at 10°C within 4 hours.
Add to the solution 604 parts of disproportionated rosin and 14 parts of
Post-stir at 15-18° C. for an hour. After stirring according to Example 1, 625 parts of SZ111 and a transparent resin having a softening point of about 90-100 DEG C. are obtained. (b) Preparation of resin-phenol-glycerin ester 367 parts of the resin-phenol-compound described in (a) are heated in a stirred vessel in the presence of 5 parts of tin powder at 230°C within 8 to 10 hours while distilling off the reaction water. Esterify with 92 parts of glycerin to a SZ of about 25 at 250°C to 250°C with simultaneous passage of nitrogen. (c) Production of resin-phenol-glycerin ester-oxyethylate 438 parts of the resin-phenol-glycerin ester described in (b) was added with 3.3 parts of sodium hydroxide, stirred in an airtight container, and fed with 550 parts of ethylene oxide. Oxyethylation is carried out at 150-170° C. while maintaining a pressure of 1.5-2.5 bar. When all the ethylene oxide is forced in, it is then stirred for 1 hour at 150-160°C. The resulting resin-oxyethylate is viscous, brown in color and contains 12.5 moles of ethylene oxide. Its cloud point in 25% butyl diglycol solution is 60°C. Example 11 (a) Preparation of resin-naphthol derivative 106 parts of boron trifluoride-ethyl ether complex salt
It is added within 4 hours at 10 DEG C. to a solution of 604 parts of rosin and 203.2 parts of β-naphthol in 600 parts of tetrachloromethane and stirred for 14 hours at 15 DEG -18 DEG C. After working up according to Example 1, 726.3 parts of a transparent resin having an SZ of 144.5 and a softening point of about 115-120 DEG C. are obtained. (b) Preparation of resin-naphtholglycerol ester 403.6 parts of the modified resin described in (a) are heated in a stirred vessel in the presence of 5.3 parts of tin powder at 230°C to 250°C within 8 to 10 hours while distilling off the reaction water. Under simultaneous conduction of nitrogen
Esterified with 92 parts of glycerin to SZ approximately 25. (c) Manufacture of resin-naphthol-glycerin ester-oxyethylate 477 parts of the resin-naphthol-glycerin ester described in (b) was stirred in an airtight container and heated at 150 to 160° C. under pressure 2 while feeding 660 parts of ethylene oxide.
Oxyethylation is carried out at a pressure of between 8 and 8 bar. When all the ethylene oxide is forced in, it is then stirred for 1 hour at 150-160°C. The resulting resin acid glycerol ester adduct contains 15 moles of ethylene oxide. It is viscous, brown in color and 25
% butyl diglycol solution is 58°C. Example 12 (a) Preparation of resin-guaiacol-derivatives 25% solution of boron trifluoride in guaiacol 264.5
of tetrachloromethane at 10°C within 4 hours.
Add to a solution of 604 parts of rosin in 800 parts and for 14 hours
Post-stir at 15-18°C. After working up according to Example 1, 630 parts of a transparent resin having an SZ of about 101 and a softening point of about 110° C. are obtained. (b) Preparation of resin acid-glycerin ester 403.6 parts of the modified resin described in (a) are heated in a stirred vessel in the presence of 5.3 parts of tin powder at 230°C to 250°C within 8 to 10 hours while distilling off the reaction water. Under simultaneous conduction of nitrogen
Esterified with 92 parts of glycerin to SZ approximately 25. (c) Production of resin acid-glycerol ester-oxyethylate 477 parts of the resin acid glycerol ester described in (b) was added with 3.4 parts of sodium methylate, stirred in an airtight container, and fed with 660 parts of ethylene oxide. Oxyethylation is carried out at a temperature of 2 to 3 bar and then 1.3 to 3 bar.
150 for 1 hour when all ethylene oxide is injected
Post-stir at 160°C. The resulting resin acid glycerol ester adduct is viscous, brown in color and contains 15 moles of ethylene oxide. The cloud point for a 25% butyl diglycol solution is 63.5°C. Example 13 477 parts of resin acid glycerol ester prepared according to Example 12(b) were mixed with 3300 parts of ethylene oxide according to Example 12(c).
react with the part. The resulting yellow-brown resin acid-monoglycerol ester adduct is waxy and contains 75 moles of ethylene oxide. A 25% butyl diglycol solution has a cloud point of 101-102°C. Example 14 (a) Preparation of benzyl-resin-glycerin ester 302 parts of rosin in 126.5 parts of benzyl chloride are heated gradually to 100 DEG C. under nitrogen after addition of 0.4 part of zinc chloride and kept at this temperature for 2 hours. As soon as the evolution of hydrogen chloride subsides, the temperature is increased to 200°C and held at 200-210°C for about 1 hour until the reaction product is virtually halogen-free. about
After cooling to 100° C. and adding 92 parts of glycerin and 130 parts of xylene, the mixture is heated to boiling under reflux, and the reaction water is azeotropically distilled and collected in a water separator. After 4 hours the reaction is complete and the volatile components are removed by vacuum distillation or by rotary evaporation. SZ30 as residue
A light-colored resin having a softening point of 120 to 125° C. is obtained. (b) Preparation of resin-oxyethylate 465 parts of the benzyl-resin-glycerin ester described in (a) are oxyethylated with 600 parts of ethylene oxide after addition of 3.4 parts of sodium methylate. The resulting viscous resin-glycerol adduct is brown in color and contains 13.6 moles of ethylene oxide. The cloud point in a 25% butyl diglycol solution is 58.5°C. Example 15 465 parts of benzyl resin-glycerin ester prepared according to Example 14(b) are reacted with 1496 parts of ethylene oxide after addition of 3.4 parts of sodium methylate. The resulting resin-oxyethylate contains 34 moles of ethylene oxide. It is waxy, brown in color and its cloud point in 10% saline solution is 61.5°C. Example 16 465 parts of benzyl-resin-glycerin ester prepared according to Example 14(b) are reacted with 2706 parts of ethylene oxide after addition of 3.4 parts of sodium methylate.
The resulting resin-oxyethylate contains 61.5 moles of ethylene oxide. The appearance corresponds to the product of Example 15 and its cloud point in 10% saline solution is 56.5
It is ℃. Example 17 (a) Preparation of resin-phenol-glycerin ester 302 parts of rosin are heated with 128 parts of 4-chlorophenol together with 0.4 part of zinc chloride, gradually heated to 100 DEG C. under nitrogen and kept at this temperature for 2 hours.
As soon as the evolution of hydrogen chloride decreases, reduce the temperature to 200
C. and at 200-210.degree. C. for about 1 hour until the reaction product is virtually halogen-free.
keep. After cooling to 100°C and adding 92 parts of glycerin and 130 parts of xylene, heat to boiling under reflux;
The reaction water is azeotropically distilled and collected in a water separator. Approximately 4
After a period of time, the reaction is complete and the volatile components are removed by vacuum distillation or in a rotary evaporator. A light colored resin with a SZ25 and a softening point of 120-125° C. is obtained as a residue. (b) Preparation of resin-oxyethylate 468.5 parts of the resin-phenol-glycerin ester described in (a) was stirred in an airtight container with the addition of 2.4 parts of sodium hydroxide and 616 parts of ethylene oxide was added.
Oxyethylation is carried out at 140-150° C. while maintaining a pressure of 2.5-3.5 bar. When all the ethylene oxide is forced in, the mixture is stirred for 1 hour at 140-150°C. The resulting viscous resin-glycerol adduct is reddish-brown in color and contains 14 moles of ethylene oxide. The cloud point for a 25% butyl diglycol solution is 60°C. Example 18 (a) Preparation of a resin-phenol derivative 302 parts of rosin are heated with 128 parts of 4-chlorophenol and, after addition of 0.4 part of zinc chloride, gradually heated to 100 DEG C. under nitrogen and kept at this temperature for 2 hours.
Subsequently, the temperature is increased from 200°C to 210°C until the reaction product is halogen-free after about 1 hour.
Increase to ℃. After cooling, a light colored resin is obtained with a softening point of about 105°C. (b) Production of resin-oxyethylate Resin-phenol-compounds 393.5 as described in (a)
part is oxyethylated according to Example 17(b) at 140-150°C after addition of 2.1 parts of sodium hydroxide. The resulting low viscosity resin-phenol-adduct is olive green and contains ethylene oxide.
Contains 12 moles. The cloud point for butyl diglycol is 50.5°C. Example 19 (a) Preparation of a resin-cresol-glycerin ester 302 parts of rosin are condensed according to Example 17(a) with 5-chloro-2-hydroxytoluene in the presence of 0.4 parts of zinc chloride and subsequently esterified with 92 parts of glycerin. do. SZ24 as residue and softening point 110
A light-colored resin having a temperature of 115°C to 115°C is obtained. (b) Preparation of the resin-oxyethylate 478 parts of the resin-cresol-glycerin ester described in (a) are reacted with 660 parts of ethylene oxide according to Example 17(b) after addition of 2.5 parts of sodium hydroxide. The resulting viscous resin-glycerol adduct contains 15 moles of ethylene oxide. The cloud point for a 25% butyl diglycol solution is 60°C. Example 20 (a) Production of resin-naphthol-glycerin ester 302 parts of rosin was mixed with 4-chloro-1-naphthol.
After addition of 489.4 parts of zinc chloride and 0.4 parts of zinc chloride, it is condensed according to Example 17(a) and esterified with 92 parts of glycerin. After removal of volatile components a brown resin with SZ29 and a softening point of 115-125°C is obtained. (b) Preparation of the resin-oxyethylate 489 parts of the resin-naphthol-glycerol ester described in (a) are added with 2.5 parts of sodium hydroxide and then reacted with 772 parts of ethylene oxide according to Example 17(b). The resulting viscous resin-glycerol adduct is reddish-brown in color and contains 18 moles of ethylene oxide. The cloud point for a 25% butyl diglycol solution is 59°C. In the following table, quantitative confirmation results of the compounds prepared according to Examples 1 to 20 above are shown.

[Table] In the following table, the surface activity is listed according to the following DIN-standard. Wetting power: DIN No. 53901, Foaming power: DIN No.
No. 53902, surface tension: DIN No. 53914 and iodine color number: DIN No. 6162. The foaming power is evaluated according to the following classification: 0: none, 1: weak, 2: weak - medium, 3: medium. and 4. Significant foaming.

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Claims (1)

[Claims] 1 General formula A[(X-O)n-H]m (wherein A represents rosin or disproportionated rosin, phenol, guaiacol, salicylic acid, o-, m-
and an aromatic hydroxy compound selected from the group consisting of p-cresol and β-naphthol, or selected from the group consisting of 4-chlorophenol, 5-chloro-2-hydroxytoluene, 4-chloro-1-naphthol and benzyl chloride. indicates the residue of a natural resin acid modified by oxyarylation obtained by reacting a halogen-eliminating aryl- or aralkyl-compound with the addition of a polycyclic system to the double bond; or represents a residue of a glycerin ester of these modified natural resin acids, where X is a group of the formula _-CH2CH2- , n is a number from about 3 to ₄₀ , and the total number of n is a number from about 8 to 75. where m is 2 or 3). 2 General formula A[(X-O)n-H]m (wherein A represents rosin or disproportionated rosin with phenol, guaiacol, salicylic acid, o-, m-
and an aromatic hydroxy compound selected from the group consisting of p-cresol and β-naphthol, or selected from the group consisting of 4-chlorophenol, 5-chloro-2-hydroxytoluene, 4-chloro-1-naphthol and benzyl chloride. indicates the residue of a natural resin acid modified by oxyarylation obtained by reacting a halogen-eliminating aryl- or aralkyl-compound with the addition of a polycyclic system to the double bond; or represents a residue of a glycerin ester of these modified natural resin acids, where X is a group of the formula _-CH2CH2- , n is a number from about 3 to ₄₀ , and the total number of n is a number from about 8 to 75. and m is 2 or 3).
nm mol (n and m have the meanings given above) of a compound of the general formula A-(H)m (wherein A and m have the meanings given above) and which have free hydroxy- and optionally carboxyl groups. ) with ethylene oxide while etherifying or esterifying the functional group. 3 General formula A[(X-O)n-H]m (wherein A represents rosin or disproportionated rosin with phenol, guaiacol, salicylic acid, o-, m-
and an aromatic hydroxy compound selected from the group consisting of p-cresol and β-naphthol, or selected from the group consisting of 4-chlorophenol, 5-chloro-2-hydroxytoluene, 4-chloro-1-naphthol and benzyl chloride. indicates the residue of a natural resin acid modified by oxyarylation obtained by reacting a halogen-eliminating aryl- or aralkyl-compound with the addition of a polycyclic system to the double bond; or represents a residue of a glycerin ester of these modified natural resin acids, where X is a group of the formula _-CH2CH2- , n is a number from about 3 to ₄₀ , and the total number of n is a number from about 8 to 75. m is 2 or 3) A surfactant containing a natural resin acid derivative represented by: